EP0339674A2 - Method of bleaching cotton garments and abradable pellets for use therein - Google Patents
Method of bleaching cotton garments and abradable pellets for use therein Download PDFInfo
- Publication number
- EP0339674A2 EP0339674A2 EP89107785A EP89107785A EP0339674A2 EP 0339674 A2 EP0339674 A2 EP 0339674A2 EP 89107785 A EP89107785 A EP 89107785A EP 89107785 A EP89107785 A EP 89107785A EP 0339674 A2 EP0339674 A2 EP 0339674A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- bleaching
- permanganate
- garments
- agent
- pellets
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000008188 pellet Substances 0.000 title claims abstract description 20
- 229920000742 Cotton Polymers 0.000 title claims abstract description 12
- 238000004061 bleaching Methods 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 25
- 239000007844 bleaching agent Substances 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 19
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 13
- 239000011707 mineral Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 239000004575 stone Substances 0.000 claims description 29
- 239000004568 cement Substances 0.000 claims description 26
- 239000010440 gypsum Substances 0.000 claims description 25
- 229910052602 gypsum Inorganic materials 0.000 claims description 25
- 239000002969 artificial stone Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 13
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical group OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 8
- 239000012764 mineral filler Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229940099408 Oxidizing agent Drugs 0.000 claims 5
- 238000009826 distribution Methods 0.000 claims 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims 1
- 229910001388 sodium aluminate Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 241000219146 Gossypium Species 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000008262 pumice Substances 0.000 description 8
- 239000011398 Portland cement Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 229960001841 potassium permanganate Drugs 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- 238000009740 moulding (composite fabrication) Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- -1 for example Substances 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229960005076 sodium hypochlorite Drugs 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011507 gypsum plaster Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000007686 potassium Nutrition 0.000 description 2
- 229960003975 potassium Drugs 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 235000014441 Prunus serotina Nutrition 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 241001412173 Rubus canescens Species 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- IQYKECCCHDLEPX-UHFFFAOYSA-N chloro hypochlorite;magnesium Chemical compound [Mg].ClOCl IQYKECCCHDLEPX-UHFFFAOYSA-N 0.000 description 1
- 229940000425 combination drug Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229940074415 potassium silicate Drugs 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- PYILKOIEIHHYGD-UHFFFAOYSA-M sodium;1,5-dichloro-4,6-dioxo-1,3,5-triazin-2-olate;dihydrate Chemical compound O.O.[Na+].[O-]C1=NC(=O)N(Cl)C(=O)N1Cl PYILKOIEIHHYGD-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P7/00—Dyeing or printing processes combined with mechanical treatment
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/13—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using inorganic agents
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/15—Locally discharging the dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/15—Locally discharging the dyes
- D06P5/153—Locally discharging the dyes with oxidants
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/15—Locally discharging the dyes
- D06P5/158—Locally discharging the dyes with other compounds
Definitions
- the field of the invention is the treatment of dyed bleachable cotton garments with abrading and/or bleaching agents to produce a "frosted" appearance.
- Another alternative which has also received some degree of commercial use is to employ a loose mix-mixture of a bleaching agent with an inert buy somewhat abrasive filler, such as, for example, potassium permanganate powder and fine quarts sand or other siliceous material.
- abrasive filler such as, for example, potassium permanganate powder and fine quarts sand or other siliceous material.
- the frosting effect obtained from such a free-flowing mixture is rather “flat" and is considered to be less attractive.
- Potassium permanganate and other bleaching agents have been encapsulated or adsorbed on support materials or embedded in formed bodies for other purposes. See, for example, United States Patents 3,535,262, 4,279,764, 4,460,490, 4,665,782, 4,657,784, and 4,711,748.
- German Patent 2,311,964 describes the preparation of a product for decontaminating radioactive waste containing manganese dioxide (MnO2) in Plaster of Paris (gypsum).
- MnSO4 manganese sulfate
- KMnO4 potassium permanganate
- the MnSO4 and KMnO4 react in the slurry to form the MnO2, which is dispersed throughout the gypsum mass and removes radionuclides by adsorption.
- This invention provides a greatly improved method of frosting dyed bleachable cotton garments.
- natural pumice stones especially prepared artificial stones are employed.
- the artificial stones are composed of cemented aggregates of mineral particles which provide abradable surfaces.
- a bleaching agent is dispersed throughout the stones, being embedded in the cemented aggregate.
- this bleaching agent which is preferably an alkali metal permanganate, occurs in the form of fine to microscopic particles rather than being present as an aqueous solution as in prior prac tice.
- the artificial stones can be shipped and stored after manufacture without concern about the leaking of bleach solution. They will retain their capacity to provide a gradual bleaching action. Initial overbleaching or subsequent underbleaching is avoided. Last, but not least, this product takes much of the drudgery out of the garment frosting operation and eliminates most of the hazards normally associated with the handling of bleaching agents in their concentrated forms.
- the artificial stones of this invention are especially suitable for use with potassium permanganate (KMnO4) and sodium permanganate (NaMnO4) as the bleaching agents.
- K2MnO4 potassium or other alkali metal manganates
- Chlorine-based bleaching agents can also be used, including sodium hypochlorite or other alkali metal hypochlorites.
- Other active chlorine-releasing bleaching agents which can be used include organic halogen bleaches, for example, chlorocyanurates. Of this class, sodium dichloroisocyanurate dihydrate is preferred.
- the bleaching agent is added to the cement formulation in either solid or liquid form, i.e., as an aqueous solution.
- KMnO4 and sodium dichloroisocyanurate are preferably added as particulate solids, whereas in the case of sodium permanganate and sodium hypochlorite, addition as a solution is preferred.
- liquid addition the use of a hydrable self-curing cement is preferred, as will subsequently be described. Even though the bleaching agent is added as an aqueous solution, the water-binding action of the cement can leave most of the bleaching agent as highly dispersed solid particles.
- bleaching agents other than potassium or sodium permanganate i.e., sodium hypochlorite and sodium dichlorocyanurate dihydrate
- their performance is at a much lower level than those of permanganate-containing formulations.
- the preferred choices for high-intensity frosting are combinations of sodium or potassium permanganate in either gypsum of magnesia cements. Where low bleaching intensities are desired (such as in chemically enhanced stone washing), combinations of Na or K permanganate with Portland cement - preferably white cement - can be used.
- the artificial stones of this invention are prepared with abradable surfaces. More specifically, they comprise cemented aggregates of mineral particles with a bleaching agent embedded therein, which is preferably in particulate form.
- the bleaching agent may be mixed dry or as an aqueous solution with the aggregate material, and may be self-curing in cemented form, or there may be included a binder in addition to the aggregate material. An appropriate amount of water is added to the mix.
- the stones can be formed from low moisture mixes, which may be a paste or thick slurry, which can be formed into the stones by forming processes, such as extrusion, molding, agglomeration, etc.
- a preferred major component of the stones' matrix material is a self-curing inorganic cement.
- Gypsum Pullaster of Paris
- Hydratable gypsum may be used in a similar form as for preparing gypsum wallboard. When mixed with a small amount of water the gypsum will hydrate and set to an integrated solid body.
- the hydratable gypsum powder with the particulate bleaching agent, adding a small amount of water to form a thick paste, the artificial stones can be formed with the agent particles dispersed therethrough essentially in encapsulated or embedded form. Even though the porosity of the artificial stones is limited, the bleaching agent can be progressively released by surface abrasion.
- gypsum in the hemihydrate form, is a rapid setting material, allowing only a very limited time for forming into pellets. Specifically when using extrusion as the aggregation method, the hydration of gypsum is accelerated by the addition of permanganate. The setting rate can be controlled by addition of one or more decelerants, to allow time to mix and form the material into pellets prior to setting.
- Commercially available slow-set gypsums are usually retarded by addition of an organic component, e.g., citric acid or hydrolyzed protein, which are attacked by the oxidizing agent.
- the retardants used for this purpose should be inorganics such as H3PO4, NaH2PO4, Ca(H2PO4)2, Na2B4O7, etc. Elevated temperature and pressure are also accelerants of gypsum setting, so a very dry mixture, which will generate heat and pressure when being worked, should be avoided.
- self-curing cements include the family of magnesia cements, viz., magnesium oxychloride and magnesium oxysulfate. These cements are also referred to as "Sorel" cements. Further usable cements also include Portland cement (white Portland cement is especially desirable because of its low iron content), Pozzolan cement, calcium aluminate cement, and related cements.
- An advantage of forming the stones from a self-curing of hydratable cement is that the cement component provides sufficient abrasive action so that the fabric is subjected simultaneously to both bleaching and abrasion.
- mineral filler can be used in combination with the binder.
- the stones may be composed of an abrasive mineral filler united by an inorganic binder, and the particulate or liquid bleaching agent may be distributed therethrough in the same manner as described for the self-curing cement type of stones.
- a preferred inorganic binder is sodium silicate (water glass) or potassium silicate. Alternatively, sodium or other alkali metal or water-soluble aluminate binders can be used.
- the abrasive mineral fillers may be selected from a wide variety of materials including clays, diatomaceous earth, ground pumice, precipitated silica, fine quartz sand, finely-divided perlite, natural or synthetic zeolites, etc.
- the bleach-containing solidified cements are formed into suitable lump or pellet form, comprising the artificial stones.
- the stone size and form can influence the bleaching pattern obtainable in the frosting step. Given comparable tumbling times, the regularity and uniformity of the bleach effect increases with decreasing stone size. Conversely, the larger the stone, the more spotty and irregular the bleached areas become.
- Preparation of stones of various sizes can be achieved in a number of ways.
- the bleach-containing cement paste can be poured into molds of a variety of shapes and sizes. For example, large slabs of 0.5 to 1.5 inches thickness can be formed, and then cut into rectangular or square pieces of 1" to 1.5" side length, or any other desirable dimension.
- the slabs can be mechanically crushed to give irregular shaped lumps, with desirable size ranges to be separated out by a classifier.
- the cement paste can be poured directly into individual molds of the desired shape and size.
- the water content of the paste should be slightly higher (to make it pourable) than for the aggregation methods described below.
- Stones suitable for frosting or garments can also be made by extrusion, disk pelletization, briquetting, tabletting, or other methods familiar to those skilled in the art.
- a slow setting gypsum material (preferred 80 to 90 parts) are mixed with 5 to 15 parts of KMnO4 and 0 to 25 parts of a thickener (preferred 0 to 10 parts), and water sufficient to form a stiff dough.
- This dough can then be formed into pellets by any method familiar to those skilled in the art; for example, by extrusion, or by rolling between textured rolls, or by pelletization, etc. Once formed, the pellets are self-drying and self-hardening due to the rehydration and setting of the gypsum.
- the amount of KMnO4 used is an added control of bleaching intensity, along with tumbling time, and weight ratio or garments to pellets selected during the "frosting" step of this process.
- a measured quantity of crystalline or powdered potassium permanganate is dry mixed with a predetermined amount of filler. After a homogeneous blend is obtained, a predetermined quantity of binder plus the proper amount of water is worked in the mixture so that an extrudable mass is obtained. This, in most cases, represents a still powdery but slightly cohesive material. The mass is then extruded to form 1/4" to 1/2" diameter rounds of about 3/4" to 1-1/2" in length. The sizes and shapes of the product are selected for convenience and maximum production rate. Diameters of about 1/16" or even less or of 1" or more are possible. Instead of rounds, other geometrical shapes such as triangular, rectangular, or stars can be used. After extrusion, the product is cured at either ambient or elevated temperature (60 - 110°C). Curing at higher temperatures produces products of higher hardness and with slower release characterization.
- the extruded product containing about 10% KMnO4 (or about 12% K2MnO4) is tumbled with damp denim garments for a period of 5 to 25 minutes.
- the weight ratio between the quantity of frosting agent and dry garment weight may range from 3 to 0.1, depending on the degree of bleaching desired.
- the extruded pellets are abraded, being finally reduced to a powder.
- the garments make a large number of contacts with the permanganate-containing extrudates of various sizes, whereby each contact produces localized bleaching action.
- the garments are treated with a reducing agent - commonly sodium metabisulfite - to remove the brown stains of manganese dioxide.
- 89 lb gypsum was mixed with 1 lb Ca(H2PO4)2 (to retard hydration) and 10 lb KMnO4 crystals, forming a uniform dry blend. Water was added to this blend in a high shear mixer to form a wet dough, which was then extruded through a die plate having 1/2" square holes. The soft pellets formed were fed onto a moving belt to set.
- 89 lb gypsum was mixed with 1 lb Na2B4O7 retardant and 10 lb KMnO4 crystals to a uniform dry blend, which was then mixed with water to form a wet dough.
- the dough was extruded through 1/2" square holes, forming soft pellets on a moving belt. These pellets were sprayed with a 10% K2SO4 solution to accelerate the gypsum set.
- the reaction of the gypsum hemihydrate to dihydrate absorbed most of the water form the system, and the heat of hydration drives off most of the rest. Hard, dry pellets were formed.
- a frosting test with this product (50 g frosting agent with 60 g blue denim tumbled for 30 minutes) showed high intensity, high contrast bleaching.
Abstract
Description
- The field of the invention is the treatment of dyed bleachable cotton garments with abrading and/or bleaching agents to produce a "frosted" appearance.
- In the United States, and, in fact, throughout the world, there is a large demand for cotton denim garments which have a distinctly faded, partially worn appearance. These garments are referred to as "frosted", "iced", "whitewashed", or "acid-washed". Although cotton denim accounts for the bulk of the "frosted" fabrics, other cotton materials, such as different types of twills and cotton corduroys, are also subject to frosting.
- It has been known for many years to use abrasive materials, such as pumice, to "stone-wash" dyed cotton twills to create a preworn appearance. More recently, this "worn" or "distressed" look has become particularly fashionable in apparel made from denim or similar cotton fabric, which has usually been dyed a bluish to black color. Earlier processing consisted primarily of dry tumbling the cotton garments with a quantity of pumice stones in commercial washing machines so that part of the dye was mechanically removed from the fabric. However, a non-abrasive bleaching process for "bluejeans" has been proposed (United States Patent 4,218,220). Currently, the "bluejean" industry's preference is for methods which include mechanical abrasion in combination with chemical bleaching.
- In one industry practice, natural pumice stones, which are porous, are presoaked in an aqueous solution of an oxidizing-type bleaching agent. United States patent 4,740,213 discloses this procedure with particular reference to sodium hypochlorite impregnation of the pumice. There is currently an industry preference for potassium permanganate as the impregnating bleach. Hypochlorite tends to damage the fabric. Residual manganese dioxide from permanganate bleaching can be removed with a neutralizing agent, such as sodium bisulfite.
- In the use of natural pumice stones presoaked in an aqueous solution of a bleaching agent, several practical disadvantages have been encountered. Even though the stones are drained of excess solution, they can continue to release the bleaching solution by seepage during storage. Further, the initial contacting of the stones with the moist denim garments can result in overbleaching. As the treatment continues the degree of bleaching decreases. Such irregular bleaching can result in a streaked, unattractive appearance. Moreover, the bleach solution is substantially exhausted with each use of the stones, and they must be resoaked frequently.
- Several improvements have been proposed. In one procedure which is being used commercially to some extent, the natural pumice stones are preimpregnated under pressure/vacuum conditions, the details of which are not known. This preparation treatment may provide for a greater degree of impregnation, and more use of the stones without recharging. However, these stones do continue to exude solution on standing, and the initial use of the stones can result in spotty bleaching which is generally undesirable.
- Another alternative which has also received some degree of commercial use is to employ a loose mix-mixture of a bleaching agent with an inert buy somewhat abrasive filler, such as, for example, potassium permanganate powder and fine quarts sand or other siliceous material. The frosting effect obtained from such a free-flowing mixture is rather "flat" and is considered to be less attractive.
- Potassium permanganate and other bleaching agents have been encapsulated or adsorbed on support materials or embedded in formed bodies for other purposes. See, for example, United States Patents 3,535,262, 4,279,764, 4,460,490, 4,665,782, 4,657,784, and 4,711,748. German Patent 2,311,964 describes the preparation of a product for decontaminating radioactive waste containing manganese dioxide (MnO₂) in Plaster of Paris (gypsum). A slurry is formed from manganese sulfate (MnSO₄) and potassium permanganate (KMnO₄) and gypsum which is cast into blocks. The MnSO₄ and KMnO₄ react in the slurry to form the MnO₂, which is dispersed throughout the gypsum mass and removes radionuclides by adsorption.
- This invention provides a greatly improved method of frosting dyed bleachable cotton garments. Instead of natural pumice stones, especially prepared artificial stones are employed. In accordance with the present invention, the artificial stones are composed of cemented aggregates of mineral particles which provide abradable surfaces. A bleaching agent is dispersed throughout the stones, being embedded in the cemented aggregate. Thus, this bleaching agent, which is preferably an alkali metal permanganate, occurs in the form of fine to microscopic particles rather than being present as an aqueous solution as in prior prac tice.
- When the garments are tumbled in moist condition in contact with the artificial stones, exterior surfaces of the stones abrade, gradually releasing the bleaching agent. Light to moderate to high contrast bleaching can be produced without overbleaching and without fiber damage, and the stones can be reused repeatedly until they completely disintegrate.
- The artificial stones can be shipped and stored after manufacture without concern about the leaking of bleach solution. They will retain their capacity to provide a gradual bleaching action. Initial overbleaching or subsequent underbleaching is avoided. Last, but not least, this product takes much of the drudgery out of the garment frosting operation and eliminates most of the hazards normally associated with the handling of bleaching agents in their concentrated forms.
- The artificial stones of this invention are especially suitable for use with potassium permanganate (KMnO₄) and sodium permanganate (NaMnO₄) as the bleaching agents. However, they can be advantageously used with other bleaching agents, including potassium or other alkali metal manganates, such as K₂MnO₄. Chlorine-based bleaching agents can also be used, including sodium hypochlorite or other alkali metal hypochlorites. Other active chlorine-releasing bleaching agents which can be used include organic halogen bleaches, for example, chlorocyanurates. Of this class, sodium dichloroisocyanurate dihydrate is preferred. The bleaching agent is added to the cement formulation in either solid or liquid form, i.e., as an aqueous solution. KMnO₄ and sodium dichloroisocyanurate are preferably added as particulate solids, whereas in the case of sodium permanganate and sodium hypochlorite, addition as a solution is preferred. With liquid addition, the use of a hydrable self-curing cement is preferred, as will subsequently be described. Even though the bleaching agent is added as an aqueous solution, the water-binding action of the cement can leave most of the bleaching agent as highly dispersed solid particles.
- Even though some bleaching agents other than potassium or sodium permanganate, i.e., sodium hypochlorite and sodium dichlorocyanurate dihydrate, function as active ingredients in the artificial frosting stones, their performance is at a much lower level than those of permanganate-containing formulations. The preferred choices for high-intensity frosting are combinations of sodium or potassium permanganate in either gypsum of magnesia cements. Where low bleaching intensities are desired (such as in chemically enhanced stone washing), combinations of Na or K permanganate with Portland cement - preferably white cement - can be used.
- The artificial stones of this invention are prepared with abradable surfaces. More specifically, they comprise cemented aggregates of mineral particles with a bleaching agent embedded therein, which is preferably in particulate form. The bleaching agent may be mixed dry or as an aqueous solution with the aggregate material, and may be self-curing in cemented form, or there may be included a binder in addition to the aggregate material. An appropriate amount of water is added to the mix. The stones can be formed from low moisture mixes, which may be a paste or thick slurry, which can be formed into the stones by forming processes, such as extrusion, molding, agglomeration, etc.
- A preferred major component of the stones' matrix material is a self-curing inorganic cement. Gypsum (Plaster of Paris) is particularly desirable. Hydratable gypsum may be used in a similar form as for preparing gypsum wallboard. When mixed with a small amount of water the gypsum will hydrate and set to an integrated solid body. By premixing the hydratable gypsum powder with the particulate bleaching agent, adding a small amount of water to form a thick paste, the artificial stones can be formed with the agent particles dispersed therethrough essentially in encapsulated or embedded form. Even though the porosity of the artificial stones is limited, the bleaching agent can be progressively released by surface abrasion.
- Depending on the method of aggregation chosen, various commercial forms of gypsum may be used. Unformulated gypsum, in the hemihydrate form, is a rapid setting material, allowing only a very limited time for forming into pellets. Specifically when using extrusion as the aggregation method, the hydration of gypsum is accelerated by the addition of permanganate. The setting rate can be controlled by addition of one or more decelerants, to allow time to mix and form the material into pellets prior to setting. Commercially available slow-set gypsums are usually retarded by addition of an organic component, e.g., citric acid or hydrolyzed protein, which are attacked by the oxidizing agent. The retardants used for this purpose should be inorganics such as H₃PO₄, NaH₂PO₄, Ca(H₂PO₄)₂, Na₂B₄O₇, etc. Elevated temperature and pressure are also accelerants of gypsum setting, so a very dry mixture, which will generate heat and pressure when being worked, should be avoided.
- Other self-curing cements include the family of magnesia cements, viz., magnesium oxychloride and magnesium oxysulfate. These cements are also referred to as "Sorel" cements. Further usable cements also include Portland cement (white Portland cement is especially desirable because of its low iron content), Pozzolan cement, calcium aluminate cement, and related cements.
- An advantage of forming the stones from a self-curing of hydratable cement is that the cement component provides sufficient abrasive action so that the fabric is subjected simultaneously to both bleaching and abrasion. When a binder is used which is not itself abrasive, mineral filler can be used in combination with the binder. The stones may be composed of an abrasive mineral filler united by an inorganic binder, and the particulate or liquid bleaching agent may be distributed therethrough in the same manner as described for the self-curing cement type of stones. A preferred inorganic binder is sodium silicate (water glass) or potassium silicate. Alternatively, sodium or other alkali metal or water-soluble aluminate binders can be used. The abrasive mineral fillers may be selected from a wide variety of materials including clays, diatomaceous earth, ground pumice, precipitated silica, fine quartz sand, finely-divided perlite, natural or synthetic zeolites, etc.
- Representative formulations of the artificial stones are set out below.
General Formulas for Artificial Stones Formed from Self-Curing Cements Ingredients Wt. % Range Preferred Wt. % Cement 70 - 99.5 85 - 90 Bleaching agent 0.5 - 30 10 - 15 Formulas for Artificial Stones Produced from Mineral Fillers and Inorganic Binders Ingredients Wt. % Range Preferred Wt. % Bleaching agent 5 - 25 10 - 15 Mineral binder 3 - 20 5 - 10 Mineral Filler 55 - 92 75 - 85 Water - For effective use as frosting agents, the bleach-containing solidified cements are formed into suitable lump or pellet form, comprising the artificial stones. The stone size and form can influence the bleaching pattern obtainable in the frosting step. Given comparable tumbling times, the regularity and uniformity of the bleach effect increases with decreasing stone size. Conversely, the larger the stone, the more spotty and irregular the bleached areas become. Preparation of stones of various sizes can be achieved in a number of ways. For example, the bleach-containing cement paste can be poured into molds of a variety of shapes and sizes. For example, large slabs of 0.5 to 1.5 inches thickness can be formed, and then cut into rectangular or square pieces of 1" to 1.5" side length, or any other desirable dimension. Alternatively, the slabs can be mechanically crushed to give irregular shaped lumps, with desirable size ranges to be separated out by a classifier. As another procedure, the cement paste can be poured directly into individual molds of the desired shape and size. For agglomeration by molding, the water content of the paste should be slightly higher (to make it pourable) than for the aggregation methods described below. Stones suitable for frosting or garments can also be made by extrusion, disk pelletization, briquetting, tabletting, or other methods familiar to those skilled in the art.
- For example, 60 to 95 parts of a slow setting gypsum material (preferred 80 to 90 parts) are mixed with 5 to 15 parts of KMnO₄ and 0 to 25 parts of a thickener (preferred 0 to 10 parts), and water sufficient to form a stiff dough. This dough can then be formed into pellets by any method familiar to those skilled in the art; for example, by extrusion, or by rolling between textured rolls, or by pelletization, etc. Once formed, the pellets are self-drying and self-hardening due to the rehydration and setting of the gypsum. The amount of KMnO₄ used is an added control of bleaching intensity, along with tumbling time, and weight ratio or garments to pellets selected during the "frosting" step of this process.
- This invention is further illustrated by the following examples.
- A measured quantity of crystalline or powdered potassium permanganate is dry mixed with a predetermined amount of filler. After a homogeneous blend is obtained, a predetermined quantity of binder plus the proper amount of water is worked in the mixture so that an extrudable mass is obtained. This, in most cases, represents a still powdery but slightly cohesive material. The mass is then extruded to form 1/4" to 1/2" diameter rounds of about 3/4" to 1-1/2" in length. The sizes and shapes of the product are selected for convenience and maximum production rate. Diameters of about 1/16" or even less or of 1" or more are possible. Instead of rounds, other geometrical shapes such as triangular, rectangular, or stars can be used. After extrusion, the product is cured at either ambient or elevated temperature (60 - 110°C). Curing at higher temperatures produces products of higher hardness and with slower release characterization.
- The extruded product, containing about 10% KMnO₄ (or about 12% K₂MnO₄) is tumbled with damp denim garments for a period of 5 to 25 minutes. The weight ratio between the quantity of frosting agent and dry garment weight may range from 3 to 0.1, depending on the degree of bleaching desired. In the course of the tumbling operation the extruded pellets are abraded, being finally reduced to a powder. In this manner, the garments make a large number of contacts with the permanganate-containing extrudates of various sizes, whereby each contact produces localized bleaching action.
- After completion of the frosting step, the garments are treated with a reducing agent - commonly sodium metabisulfite - to remove the brown stains of manganese dioxide.
- 89 lb gypsum was mixed with 1 lb Ca(H₂PO₄)₂ (to retard hydration) and 10 lb KMnO₄ crystals, forming a uniform dry blend. Water was added to this blend in a high shear mixer to form a wet dough, which was then extruded through a die plate having 1/2" square holes. The soft pellets formed were fed onto a moving belt to set.
- About 20 lb of water was used in forming this dough. As the gypsum hydrates, it uses about 15 lb of the water present (CaSO₄·1/2 H₂O + 1.5 H₂O→ CaSO₄ · 2 H₂O), the heat of hydration causing vaporization of part of the remaining water. Some free water apparently remained in a highly dispersed form. A hard, dry plaster pellet containing KMnO₄ crystals was obtained.
- 89 lb gypsum was mixed with 1 lb Na₂B₄O₇ retardant and 10 lb KMnO₄ crystals to a uniform dry blend, which was then mixed with water to form a wet dough. The dough was extruded through 1/2" square holes, forming soft pellets on a moving belt. These pellets were sprayed with a 10% K₂SO₄ solution to accelerate the gypsum set. The reaction of the gypsum hemihydrate to dihydrate absorbed most of the water form the system, and the heat of hydration drives off most of the rest. Hard, dry pellets were formed.
- 80 lb of slow setting gypsum was mixed with 10 lb of a clay extrusion aid and 10 lb of KMnO₄ crystals in a dry blending operation A dough was formed from this blend by addition of about 20 lb of H₂O. The presence of clay thickened the dough so that firm, tough pellets were formed on extrusion through a die plate having 1/2" diameter round holes. These pellets were self-dried and hardened as in examples II and III.
- 260 g of slow setting gypsum was intimately mixed with 72 ml of a commercial 40% solution of sodium permanganate and 30 ml of water. The resulting deep purple paste was transferred into plastic molds of about 3.5 ml volume each. The mass began to stiffen after about 20 minutes and was set after 45 minutes, at which point the gypsum castings were removed from their molds. The black cherry colored pieces contained 10.3% sodium permanganate in a highly dispersed form.
- A frosting test with this product (50 g frosting agent with 60 g blue denim tumbled for 30 minutes) showed high intensity, high contrast bleaching.
- Additional stone formulations and test results are summarized in Table A.
TABLE A Example No. Quantity & Kind of Cement Used Quantity & Kind of Bleaching Agent Used Water Used Thickening Time Set Time Hardness Results of Frosting Test VI Magnesia cement 50 g MgO + 120ml saturated MgCl₂ solution 25 g KMnO₂ (solid) - 1 hr 2.5 hr hard low intensity bleaching VII Magnesia cement 50 g MgO + 66 g MgCl₂·6 H₂O 45 mL = 63 g 40% NaMnO₄ 58 mL 1 hr 2.5 hr hard high intensity bleaching VIII 260 g Portland Cement (white) 28.9 g KMnO₄ (as solid) 84 mL 1.5 hr 6 hr very hard very low intensity bleaching IX 260 g Portland Cement (white) 52 mL = 72.8 g 40% NaMnO₄ 50 mL 10 min 1.5 hr very hard moderate intensity bleaching X 260 g Portland Cement (white) 107.7 g NaOCl solution (17% active chlorine) none 25 min 1 hr very hard low intensity bleaching XI 260 g Portland Cement (white) 28.9 g sodium dicyanurate dihydrate 125 mL 40 min 1.5 hr rough, crumbly surface low intensity bleaching
Claims (15)
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US188419 | 1988-04-29 | ||
US07/188,419 US4961751A (en) | 1988-04-29 | 1988-04-29 | Method of bleaching dyed cotton garments |
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EP (1) | EP0339674A3 (en) |
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WO2005073459A1 (en) * | 2004-02-02 | 2005-08-11 | Norberto Canelada Campos | The process of transfering dye or pigment to textile material |
WO2006026815A1 (en) | 2004-09-07 | 2006-03-16 | Bacstop Corporation Pty Ltd | Method, material and system for controlled release of anti-microbial agents |
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US5261924A (en) * | 1988-04-29 | 1993-11-16 | Carus Corporation | Layered cementitous composition which time releases permanganate ion |
US5268002A (en) * | 1989-03-10 | 1993-12-07 | Ecolab Inc. | Decolorizing dyed fabric or garments |
US5322637A (en) * | 1990-11-09 | 1994-06-21 | O'grady Richard | Composition, bleaching element, method for making a bleaching element and method for inhibiting the yellowing of intentionally distressed clothing manufactured from dyed cellulose fabric |
US5205835A (en) * | 1991-02-07 | 1993-04-27 | Fmc Corporation | Process to remove manganese dioxide from wet process denim fibers by neutralizing with peracetic acid |
US5516338A (en) * | 1995-01-25 | 1996-05-14 | Pai; Panemangalore S. | Water-soluble titanium salt-tannin dyes and methods of use thereof |
US5558676A (en) * | 1995-03-15 | 1996-09-24 | Ocean Wash, Inc. | Composition and a method for treating garments with the composition |
US5593458A (en) * | 1995-03-16 | 1997-01-14 | Ocean Wash, Inc. | Process and composition for decorating a dyed cloth fabric |
US6120554A (en) * | 1998-02-02 | 2000-09-19 | American Renewable Resources Llc | Catalyzed alkaline hydrogen peroxide bleaching of dye-containing cellulose textiles |
US6447722B1 (en) | 1998-12-04 | 2002-09-10 | Stellar Technology Company | Solid water treatment composition and methods of preparation and use |
US20030056296A1 (en) * | 2001-09-26 | 2003-03-27 | Hirsch Gary F. | Dye removal from denim scrap with a forced circulation kier |
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- 1989-04-27 NO NO89891759A patent/NO891759L/en unknown
- 1989-04-28 EP EP19890107785 patent/EP0339674A3/en not_active Withdrawn
- 1989-04-28 FI FI892056A patent/FI892056A/en not_active Application Discontinuation
- 1989-04-28 DK DK209589A patent/DK209589A/en not_active Application Discontinuation
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AU3372889A (en) | 1989-11-02 |
FI892056A (en) | 1989-10-30 |
NO891759L (en) | 1989-10-30 |
JPH01321978A (en) | 1989-12-27 |
KR890016246A (en) | 1989-11-28 |
DK209589D0 (en) | 1989-04-28 |
FI892056A0 (en) | 1989-04-28 |
US4961751A (en) | 1990-10-09 |
EP0339674A3 (en) | 1991-09-18 |
KR920001017B1 (en) | 1992-02-01 |
NO891759D0 (en) | 1989-04-27 |
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